Complexing stripping voltammetry

Precision Precision is generally limited by the uncertainty in measuring the limiting or peak current. Under most experimental conditions, precisions of+1-3% can be reasonably expected. One exception is the analysis of ultratrace analytes in complex matrices by stripping voltammetry, for which precisions as poor as +25% are possible. 

Time, Cost, and Equipment Commercial instrumentation for voltammetry ranges from less than 1000 for simple instruments to as much as 20,000 for more sophisticated instruments. In general, less expensive instrumentation is limited to linear potential scans, and the more expensive instruments allow for more complex potential-excitation signals using potential pulses. Except for stripping voltammetry, which uses long deposition times, voltammetric analyses are relatively rapid. 

The methods of investigation of metal species in natural waters must possess by well dividing ability and high sensitivity and selectivity to determination of several metal forms. The catalytic including chemiluminescent (CL) techniques and anodic stripping voltammetry (ASV) are the most useful to determination of trace metals and their forms. The methods considered ai e characterized by a low detection limits. Moreover, they allow detection of the most toxic form of metals, that is, metal free ions and labile complexes. 

Stolzberg [143] has reviewed the potential inaccuracies of anodic stripping voltammetry and differential pulse polarography in determining trace metal speciation, and thereby bio-availability and transport properties of trace metals in natural waters. In particular it is stressed that nonuniform distribution of metal-ligand species within the polarographic cell represents another limitation inherent in electrochemical measurement of speciation. Examples relate to the differential pulse polarographic behaviour of cadmium complexes of NTA and EDTA in seawater. 

Quentel et al. [294] complexed copper with l,2-dihydroxyanthraquinone-3 sulfuric acid prior to determination by absorptive stripping voltammetry in amounts down to 0.3 nM in seawater. 

Cathodic stripping voltammetry has been used to determine copper species in seawater [291,292], Van den Berg [330] determined copper in seawater by cathodic stripping voltammetry of complexes with catechol. 

Donat and Bruland [217] determined low levels of nickel and cobalt in seawater by a voltammetric technique, and the nioxime complexes of the two elements were concentrated on a hanging mercury drop electrode. The current resulting from the reduction of Co (II) and Ni (II) was measured by differential pulse cathodic stripping voltammetry. Detection limits are 6 pM (cobalt) and 0.45 nM (nickel). 

Platinum was determined in seawater by adsorptive cathodic stripping voltammetry in a method described by Van den Berg and Jacinto [531]. The formazone complex is formed with formaldehyde, hydrazine, and sulfuric acid in the seawater sample. The complex is adsorbed for 20 minutes at -0.925 V on the hanging mercury drop electrode. The detection limit is 0.04 pM platinum. 

Analysis of total zinc by anodic stripping voltammetry is problematic because of interference by the hydrogen wave in acidified samples, and due to the inability to detect organically complexed zinc at natural pH values near 8 [ 185]. An improved understanding of zinc in marine systems now requires rapid, sensitive analytical methods that are less prone to contamination, and that can be performed at sea [624],... 

Cyclohexane-1,2-dione dioxime (nioxime) complexes of cobalt (II) and nickel (II) were concentrated from 10 ml seawater samples onto a hanging mercury drop electrode by controlled adsorption. Cobalt (II) and nickel (II) reduction currents were measured by differential pulse cathodic stripping voltammetry. Detection limits for cobalt and nickel were 6 pM and 0.45 mM, respectively. The results of detailed studies for optimising the analytical parameters, namely nioxime and buffer concentrations, pH, and adsorption potential are discussed. 

Perez-Pina et al. [805] studied the use of triethanolamine and dimethyl-glyoxime complexing agents in absorptive cathodic stripping voltammetry of cobalt and nickel in seawater. Nickel and cobalt could be determined at levels down to 2 nM and 50 pM, respectively. 

Huynk et al. [218] also used differential pulse cathodic stripping voltammetry for the determination of cobalt and nickel in seawater by dimetbylgly-oxime complexation. They report detection hmits of 0.002 pg/1 for cobalt and 0.005 xg/l for nickel. 

Cathodic stripping voltammetry has been used [807] to determine lead, cadmium, copper, zinc, uranium, vanadium, molybdenum, nickel, and cobalt in water, with great sensitivity and specificity, allowing study of metal specia-tion directly in the unaltered sample. The technique used preconcentration of the metal at a higher oxidation state by adsorption of certain surface-active complexes, after which its concentration was determined by reduction. The reaction mechanisms, effect of variation of the adsorption potential, maximal adsorption capacity of the hanging mercury drop electrode, and possible interferences are discussed. 

Chloroform extraction of uranium quinoline complex Uranium adsorbed as azide on basic ion exchange column, uranium desorbed with 1 M hydrochloric acid Uranium adsorbed on bismuthol(II) modified anion exchange resin, desorbed with 0.1 M cysteine Uranium, by square wave adsorptive stripping voltammetry... 

Zinc Formation of zinc ammonium pyrrolidine dithiocarbamate complex Cathodic stripping voltammetry [619]... 

Cysteine and cystine has been determined in seawater by a method based on cathode stripping voltammetry of the copper complex [327]. 

A kind of standard additions approach can also be used for the measurement of apparent complexing capacity. In this technique, labile copper is measured by differential pulse anodic stripping voltammetry after each of a number of spikes of ionic copper have been added to the sample [420]. 

Abate G, Masini JC. Complexation of Cd(II) and Pb(II) with humic acids studies by anodic stripping voltammetry using differential equilibrium functions and discrete site models. Org. Geochem. 2002 33 1171-1182. 

J. Wang, B.S. Grabaric, Application of adsorptive stripping voltammetry for indirect measurement of nonelectroactive ions using competitive complex formation reactions, Mikrochim. Acta 100 (1990) 31-40. 

Analytical techniques such as adsorptive stripping voltammetry rely on complex formation to improve detection limits of metals such as V(IV) and V(V) [51]. An example is in the use of cupferron and KBr03 as additives to acidic aqueous solutions, which result in the adsorption of the V(V)-cupferron complex to the electrode surface that catalyzes the reduction of the Br03 ion in solution. This technique has good selectivity over Cu, Pb, Cd, Fe, and Ti, but the response is dependent on pH. 

The electrochemical behavior of Cd-oxine complexes was analyzed by square-wave stripping voltammetry [80] from the mechanistic point of view, applying the theoretical model developed previously [81-83]. Influence of ligand and reactant adsorption, and the ligand concentration on the Cd-oxine electroreduction were also examined [84] using SWV. Typical curves recorded and calculated for several Egw are shown in Fig. 5. 

Analytical Applications In addition to the above-mentioned analytical aspects of the processes at Hg electrodes, in this section, we briefly review the papers focused on the subject of the affinity of various compounds to the mercury electrode surface, which allowed one to elaborate stripping techniques for the analysis of inorganic ions. Complexes of some metal ions with surface-active ligands were adsorptively accumulated at the mercury surface. After accumulation, the ions were determined, usually applying cathodic stripping voltammetry (CSV). Representative examples of such an analytical approach are summarized as follows. 

Stripping voltammetry has been used to study the distribution of Zn(II) between labile and inert complexes in seawater with total zinc concentration of 50 nM (Muller and Kester, 1990). Formation constants of Zn(II) with various inorganic complexing agents (e.g., Cl- and N03") have been measured by anodic stripping voltammetry at total zinc concentrations of 10 nM (Komorsky-Lovrfc and Branica, 1987). 

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